Effect of Photoacid Strength on Fluorescence Modulation of 2-Naphthol Derivatives inside β-Cyclodextrin Cavity: Insights from Fluorescence, Isothermal Calorimetry, and Molecular Dynamics Simulations.

Fluorescence response of a photoacid inside a confined environment often differs markedly from the bulk response. Is there any correlation between the extent of fluorescence modulation and the strength of the photoacid? Here, we used three photoacids: 2-naphthol (2OH, p* = 3.3), 6-sulfonate-2-naphthol (6SO-2OH, p* = 3.

Photo-induced Electron Transfer or Proton-Coupled Electron Transfer in Methylbipyridine/Phenol Complexes: A Time-Dependent Density Functional Theory Investigation.

It is often difficult to assign the nature of an excited-state process unambiguously based on a limited number of experimental evidence. The methylbipyridine/phenol complex is a classic example, where experimental observations support a proton-coupled electron transfer (PCET) or a photo-induced electron transfer (PET) process. Here, we implemented time-dependent density functional theory calculation to elucidate the nature of the process.

Coumarin-Annelated Regioisomeric Heptahelicenes: Influence of Helicity on Excited-State Properties and Chiroptical Properties.

Two regioisomeric pairs of heptahelical mono- and biscoumarins that are differentiated by "" and "" disposition of the pyran-2-one moiety have been synthesized and investigated to understand the influence of helicity on excited-state and chiroptical properties. A slight variation in the helicities is found to manifest in contrasting excited-state properties of coumarin-annelated heptahelicenes; in addition to the intramolecular charge transfer, structural relaxation in the excited state is shown from theoretical calculations to cause decrease in the fluorescence quantum yield for a system with higher helicity. The optically pure enantiomers of heptahelical coumarins exhibit helicity-dependent chiroptical properties, namely, specific rotations, molar ellipticities, Cotton effects, and anisotropic dissymmetry factors.

New Insights on Hydrogen-Bond-Induced Fluorescence Quenching Mechanism of C102-Phenol Complex via Proton Coupled Electron Transfer.

The H-bonded coumarin 102 (C102)-phenol complex has been a model system usually used to understand the influence of H-bonding on photophysical processes. Zhao and Han first showed that significant H-bond strengthening occurs in the excited state and proposed the possibility of fluorescence quenching in the complex via internal conversion from a locally excited (LE) state to a low-lying charge transfer (CT) state. Later, we experimentally confirmed fluorescence quenching of C102-phenol complex in a nonpolar solvent (cyclohexane).

Helicity-Dependent Regiodifferentiation in the Excited-State Quenching and Chiroptical Properties of Inward/Outward Helical Coumarins.

Influence of helicity on the excited-state as well as chiroptical properties of two sets of regiohelical coumarins that are differentiated by "inward" and "outward" disposition of the pyran-2-one ring has been investigated. A subtle difference in the helicities manifests in divergent excited-state properties and significant differences in the dipole moments. The latter permit heretofore unprecedented regiodifferentiation in the O-H⋅⋅⋅O hydrogen-bond assisted electron-transfer quenching by phenols.

Elucidating the H-Bonding Environment of Coumarin 102 in a Phenol-Cyclohexane Mixture by Molecular Dynamics Simulation: Implications for H-Bond-Guided Photoinduced Electron Transfer.

Recently, we have experimentally demonstrated that the fluorescence intensity of coumarin 102 (C102) modulates anomalously upon hydrogen bonding to phenol in a nonpolar solvent: cyclohexane. The fluorescence intensity is first quenched gradually up to a particular mole fraction (X ≈ 0.013) but thereafter increases with further increases in the phenol mole fraction.

Modulation of ultrafast photoinduced electron transfer in H-bonding environment: PET from aniline to coumarin 153 in the presence of an inert co-solvent cyclohexane.

Despite intensive research, the role of the H-bonding environment on ultrafast PET remains illusive. For example, coumarin 153 (C153) undergoes ultrafast photoinduced electron transfer (PET) in electron-donating solvents, in both aniline (AN) and N,N-dimethylaniline (DMA), despite their very different H-bonding abilities. Thus, donor-acceptor (AN-C153) H-bonding may have only a minor role in PET (Yoshihara and co-workers, J.